US4959105A - Aluminium cleaning composition and process - Google Patents

Aluminium cleaning composition and process Download PDF

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US4959105A
US4959105A US07/493,415 US49341590A US4959105A US 4959105 A US4959105 A US 4959105A US 49341590 A US49341590 A US 49341590A US 4959105 A US4959105 A US 4959105A
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aluminum
composition
acid
debris
component
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US07/493,415
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Fred Neidiffer
Charles E. Fox
Patsy E. Fox
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/12—Light metals
    • C23G1/125—Light metals aluminium

Definitions

  • This invention relates to a composition and process useful for cleaning aluminum-containing articles. More particularly, the invention relates to a composition and process for removing debris, e.g., smut, unwanted deposit material, soil and the like, from such articles, e.g., aluminum foodstuff or beverage containers or cans.
  • debris e.g., smut, unwanted deposit material, soil and the like
  • Aluminum-containing articles are often formed into shapes using lubricants to assist in the forming process.
  • one or more lubricants are often employed in the drawing and ironing of aluminum container bodies of the type used to package foodstuffs and beverages.
  • the forming processing itself and/or the lubricant or lubricants employed produce debris, e.g., as noted above, on the article which interferes with the over-all appearance of the article. In certain instances, this debris is referred to as smut.
  • smut or smut-like material includes aluminum and/or alumina fines and/or lubricant material and/or lubricant residue. Such debris should be removed to provide an aluminum-containing article which is visually pleasing and, more importantly, make the article suitable for use, e.g., as a foodstuff or beverage container.
  • aqueous alkaline a pH of at least 10
  • an alkalinity agent present in an amount to achieve removal of aluminum fines, a complexing agent, and one or more surfactants.
  • Preferred alkalinity agents include alkali metal hydroxides and alkali metal carbonates.
  • the complexing agents are gluconic acid, citric acid, glucoheptonic acid, sodium triphosphate, EDTA, tartaric acid or the like, as well as the soluble and compatible salts thereof and mixtures thereof.
  • the relatively strong alkalinity agents employed could harm, e.g., etch, the aluminum surface unless care was exercised to control the cleaning operation.
  • Dollman U.S. Pat. No. 4,370,173 discloses removing lubricating oils and aluminum fines from aluminum surfaces using an aqueous solution of sulfuric and hydrofluoric acids and an anionic surfactant.
  • Michelson, et al U.S. Pat. No. 3,448,055 discloses removing smut from aluminum with an aqueous composition including nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and a surfactant.
  • Such solutions of strong acids are effective to clean the aluminum 15 surfaces, but also tend to etch the surface as well. Such etching is undesirable.
  • Earhart U.S. Pat. No. 4,713,119 discloses removing alkali metal aluminum silicate deposits from chemical processing equipment by alternating treatments with acidic and basic solutions.
  • the acidic solution contains sulfuric acid, sodium bisulfate, tartaric acid or phosphoric acid.
  • This patent does not disclose cleaning aluminum-containing surfaces nor that the acidic solution includes a surfactant.
  • Wood, et al U.S. Pat. No. 4,264,418 discloses removing oxide film from metals or alloys containing iron, nickel, copper, beryllium, chromium, gold, zinc, lead, or tin with a composition containing gluconic acid or its alkali metal salts, citric acid or its alkali metal salts, or tartaric acid or its alkali metal salts and, preferably, a non-ionic surfactant.
  • Aluminum-containing articles are not disclosed. Further, no "strong" acid is included in the composition.
  • Laporte, et al U.S. Pat. No. 3,306,773 discloses treating sintered aluminum parts with an aqueous alkaline solution before putting such parts into heat transfer surface.
  • Pikaar U.S. Pat. No. 3,211,659 discloses acids, such as acetic acid, EDTA, citric acid, tartaric acid, gluconic acid, glyceric acid, malic acid, glycolic acid, saccharic acid, phosphoric acid, and benzoic acid for cleaning egg shells.
  • Vinso U.S. Pat. No. 3,527,609 discloses the use of tartaric acid salts among salts of many polycarboxylic acids for use in cleaning cooling water systems. Rubin U.S. Pat. Nos.
  • 4,049,467 and 4,129,423 disclose removing manganese derived discolorations from hard surfaces by use of either dihydroxy maleic acid, dihydroxy tartaric acid, their alkali metal salts, or mixtures thereof. None of these references is concerned with relatively heavy duty cleaning of, e.g, smut removal from, aluminum surfaces.
  • Yamasoe et al U.S. Pat. No. 4,728,456 discloses an aluminum surface cleaner which is an aqueous highly acidic solution containing sulfuric acid and/or nitric acid, ferric ions, but no chromium or fluoride ions.
  • Yamasoe et al discloses that the etching of the aluminum by the sulfuric acid or nitric acid is promoted by the ferric ions.
  • Yamasoe et al discloses that chelating agents, such as citric acid and tartaric acid, can be included to accelerate the aluminum etching rate.
  • a new composition and process for cleaning debris, in particular smut, from the surface of an aluminum-containing article had been discovered.
  • This invention provides very effective and efficient cleaning, e.g., removal of debris, with little or no substantial adverse effect on, e.g., etching of, the surface being cleaned.
  • the present composition includes at least one relatively strong acid, e.g., sulfuric acid, such acid often acts as a solubilizing agent rather than as the primary cleaning agent in removing debris from the aluminum-containing surface.
  • the present composition is specifically designed to clean, and not to etch, aluminum-containing surfaces.
  • the present invention involves a process for cleaning debris from the surface of an aluminum-containing article.
  • This process comprises contacting a debris-laden aluminum-containing article with a composition comprising water, at least one polycarboxylic acid and/or at least one salt thereof, at least one acidic component in an amount effective to increase the water solubility of the polycarboxylic acid and/or salt thereof, and at least one acid acting enzyme in an amount effective to at least facilitate the removal of debris from the surface of the aluminum-containing article; and recovering the aluminum-containing article having at least a portion of the debris removed therefrom
  • the contacting occurs at conditions effective to do at least one of the following: remove at least a portion of the debris from the aluminum-containing article and condition at least a portion of the debris for removal from the aluminum-containing article.
  • the composition may also include, or all or a portion of the enzyme may be replaced by, at least one acid compatible siloxane component in an amount effective to at least facilitate the removal of at least a portion of the debris from the aluminum-containing article.
  • the composition preferably includes at least one surface active component, i.e., surfactant.
  • the use of the present- enzymes and/or the siloxane components has been found to provide enhanced aluminum cleaning without substantial adverse effects on, e.g., etching of, the surface being cleaned
  • the effective and beneficial use of enzymes in aluminum cleaning, especially in the relatively highly acidic present compositions is unexpected.
  • One particularly surprising feature of the present invention is the inclusion of acid-compatible siloxane components and the beneficial aluminum cleaning resulting therefrom.
  • other materials of the same general class, such as silanes have not been found to provide such enhanced aluminum cleaning.
  • the present compositions comprise water, at least polycarboxylic acid and/or salts thereof, at least one additional acidic component, and at least one acid acting enzyme and/or at least one acid compatible siloxane component.
  • the water often, and preferably, acts as a carrier for the other components of the composition.
  • Water preferably comprises a major amount, i.e., at least about 50%, by volume, and more preferably at least about 70% by volume, of the composition used to treat the aluminum-containing article.
  • the present compositions can be formulated at the cleaning site simply by combining the desired amounts of concentrate or concentrates and water.
  • two concentrates are prepared.
  • One concentrate includes the polycarboxylic acid and/or salts thereof and the additional acidic component in water, while the other concentrate includes the enzymes and/or the siloxane component, preferably together with one or more surfactants.
  • This is particularly useful in situations where it is difficult or impossible to include all the presently useful components in one concentrate which is substantially homogeneous, e.g., clear.
  • the surfactant mixture includes a substantially hydrocarbonaceous component, e.g., a mineral oil component, such component has only limited water solubility and does not form a homogenous concentrate with the other components of the present composition.
  • the enzyme and/or siloxane component may not form a completely homogenous concentrate with the acid components.
  • the enzyme and/or siloxane component and/or surfactant are best employed as a separate concentrate which is combined with the other components at the cleaning site when the full amount of water is present.
  • the acid acting enzymes included in the present invention are present in an amount effective to at least facilitate the removal of debris from an aluminum-containing article contacted with the enzyme-containing composition.
  • One enzyme or a combination of enzymes may be employed.
  • Acid acting enzyme means an enzyme which is effective or active in an acidic environment, in particular in the present aluminum cleaning compositions. The exact nature of the enzymatic action is not fully understood, although aluminum cleaning benefits are obtained provided that the enzyme or enzymes are effective in the relatively highly acidic compositions of the present invention.
  • Such compositions preferably have a pH in the range of about 0.5 to about 3, more preferably about 0.8 to about 2.
  • the present acid acting enzyme or enzymes act on at least a portion of the debris on the aluminum-containing article to change its character and thereby render it more easily removable from the surface of the aluminum-containing article.
  • suitable acid acting enzymes include: enzyme derived from the fermentation of B. licheniformis, such as that sold by Genecor under the trademark Rhozyme P-64; enzyme extracted from pineapple stems, such as that sold by Miles under the tradename Bromelain 1:10; and enzyme derived from the fermentation of Aspergillus niger, such as that sold by Miles under the trademark Milezyme APF-2000.
  • the amount of enzyme in the present compositions is relatively minor.
  • the enzyme is preferably present, if at all, in an amount in the range of about 0.0001% to about 0.5% by weight of the total composition. Excessive amounts of enzyme are to be avoided in view of the relatively high cost of such materials.
  • Enzyme preparations which are commercially sold often include materials other than the active enzyme, and may include as little as about 10% by weight, or even less, of the active enzyme.
  • the amounts of enzyme noted in this paragraph refer to the active enzyme.
  • the siloxane components included in the present invention are present in an amount effective to at least facilitate the removal of debris from an aluminum-containing article contacted with the siloxane component-containing composition.
  • Acid compatible siloxane component means a siloxane component which is dispersible, preferably soluble, in the present composition.
  • the present siloxane components are polymeric materials having the characteristic siloxane structure included in the polymer, e.g., the backbone of the polymer. Such polymeric materials may, and preferably do, include one or more substituents, e.g., on the siloxane repeating unit of the polymer. Such substituents may include, for example, carbon, hydrogen, oxygen and nitrogen atoms.
  • the siloxane component is preferably selected to minimize, and more preferably to substantially avoid, chemical reaction, e.g., acid/base reaction, between the siloxane component and the acid or acids of the present composition.
  • chemical reaction e.g., acid/base reaction
  • the siloxane component preferably be substantially free of reactive amino groups.
  • the siloxane component be substantially free of sulfur, in particular mercapto groups.
  • Such mercapto-containing siloxane components have been found to not provide aluminum cleaning benefits to the extent exhibited by other siloxane components.
  • the present siloxane components provide beneficial aluminum cleaning since other silicone polymers, such as the silanes, are much less effective, and even substantially ineffective, in providing enhanced aluminum cleaning. Both the siloxane components and the silane components are effective defoamers in the present compositions. This fact makes the aluminum cleaning benefits achieved with the siloxane components all the more unexpected.
  • siloxane components include: gamma-amino propyl trimethyl siloxane, such as that sold by PCR, Incorporated under the trademark Prosil 220; and gamma-methoxy-acryloxy propyl trimethyl siloxane, such as that sold by PCR, Incorporated under the trademark Prosil 248 and that sold by Dow Corning under the trademark Z-6030.
  • the amount of siloxane component in the present compositions is preferably relatively minor.
  • the siloxane component is relatively present in an amount in the range of about 0.0001% to about 0.5%, more preferably about 0.0005% to about 0.2%, by weight of the total composition. Excessive amounts of the siloxane component are to be avoided in view of the relatively high cost of such materials.
  • the polycarboxylic acid component i.e., one or more polycarboxylic acid and/or salts thereof, useful in the present invention provide substantial advantages.
  • the polycarboxylic acid component is preferably present in an amount effective to at least facilitate at least one of the following: (1) remove at least a portion of the debris from the aluminum-containing article; and (2) condition at least a portion of the debris for removal from the aluminum-containing article.
  • Polycarboxylic acid refers to a carboxylic acid having more than one functional hydroxyl group, preferably two or three functional hydroxyl groups.
  • the polycarboxylic acid component preferably includes 2 to about 10 carbon atoms per molecule.
  • this polycarboxylic acid component plays a substantial role or roles in removing debris from the aluminum-containing article.
  • the debris to be removed includes organic material, such as residues from lubricants, e.g., containing fatty acids, used in forming or shaping the aluminum-containing article.
  • the polycarboxylic acids and/or salts thereof are particularly effective in attacking this organic material, especially to reduce the ability of such organic material to adhere or cling to the aluminum-containing surface.
  • this polycarboxylic acids component is also believed to act to facilitate removing aluminum particles (which are often a part of the debris) from the surface.
  • the polycarboxylic acid component provides effective debris cleaning/conditioning action, this component is insufficiently strong or aggressive to attack the aluminum-containing surface itself.
  • the debris is removed and the aluminum-containing surface remains substantially unaffected, e.g., unetched.
  • polycarboxylic acids include: citric acid, tartaric acid, saccharic acid, maleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid, phthalic acid and the like.
  • the preferred polycarboxylic acid is tartaric acid, in particular the racemic form of tartaric acid.
  • any suitable source of polycarboxylic acid and/or salts thereof may be employed. If a salt is used, it is preferred that the salt be an ammonium salt, an alkali metal salt, an alkaline earth metal salt or mixtures thereof, more preferably an alkali metal salt.
  • a particularly useful source of tartaric acid component is cream of tartar or potassium hydrogen tartrate.
  • the polycarboxylic acid component is present in an amount effective to function as described herein.
  • the polycarboxylic acid component is present in the composition in an amount in the range of about 0.1% to about 20%, more preferably about 2% to about 15%, by weight, calculated as the polycarboxylic acid.
  • Polycarboxylic acids and/or salts thereof often have relatively limited water solubility.
  • the presently useful additional acidic component is present in an amount effective to increase the water solubility of such polycarboxylic acid component.
  • Such additional acidic component preferably is stronger, i.e., has a larger disassociation constant, than the polycarboxylic acid being employed.
  • suitable acidic components include sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, nitric acid, mixtures thereof and the like, with sulfuric acid, phosphoric acid and mixtures thereof being preferred.
  • the acidic component is present in an amount effective to solubilize aluminum fines which may be part of the debris to be removed from the aluminum-containing article.
  • the amount of acidic component included in the present composition may vary over a wide range and depend on many factors, for example, on the particular acid or acids being employed, on the particular debris to be removed, on the chemical make-up of the present composition and on the particular cleaning application involved. In certain embodiments it is preferred to include sufficient acidic component to maintain a pH in the range of about 0.5 to about 3, more preferably about 0.8 to about 2, during the contacting step.
  • the present compositions preferably include at least one surface active component or surfactant.
  • surface active component or components act to increase or enhance the effectiveness of the composition, e.g., as an aluminum cleaner.
  • the surface active component or components act to do at least one of the following: (1) assist in removing the organic portion of the debris from the surface of the aluminum-containing article; (2) aid in maintaining the homogeneity of the composition during use; and (3) aid in preventing or inhibiting redeposition of the removed debris onto the surface of the aluminum-containing article.
  • any suitable surface active component or combination of such components may be employed in the present compositions.
  • Such component is preferably nonionic or anionic, with anionic surfactants being particularly preferred.
  • the surface active component preferably has a Hydrophile-Lipophile Balance (HLB ratio), i.e., the balance of the size and strength of the hydrophilic (water-loving or polar) and lipophilic (oil-loving or non-polar) groups of the molecules, of at least about 12, more preferably in the range of about 12 to about 15.
  • HLB ratio Hydrophile-Lipophile Balance
  • Surfactants suitable for use in the practice of the present invention include, for example, those having hydrophobic groups comprising alkyl phenols, linear alcohols, branched-chain alcohols, secondary alcohols, propylene oxide/propylene glycol condensates and the like; hydrophilic groups such as ethylene oxide, ethylene oxide/ethylene glycol condensates and the like, and may further contain capping groups such as propylene oxide, chloride, benzyl chloride, amines and the like.
  • useful surfactants include free acids of complex organic phosphate esters (e.g., Gafac RP 170 from GAF Corporation); block polymers of propylene oxide and ethylene oxide (e.g., Pluonic L-61 from BASF Wyandotte, Inc.); ethoxylates of secondary alcohols containing about 11 to about 15 carbon atoms per molecule (e.g., Tergital 15-S-3 from Union Carbide Corporation); blends of linear alkyl sulfates and ethoxylates of secondary alcohols (as noted above); blends of anionic surfactants including ammonium laurel sulfate, lauramide diethanol amine, sodium laurel sarcosinate, and propyl ethyl diammonium ethosulfate; sodium linear alkyl sulfonate (e.g., Darvan No.1 from R.
  • complex organic phosphate esters e.g., Gafac RP 170 from GAF Corporation
  • a particularly useful component especially in combination with one or more other surface active components, comprises a mixture of one or more surfactants, especially anionic surfactants, such as dodecyl benzene sulfonic acid, together with at least one substantially hydrocarbonaceous material, such as paraffinic mineral oil. This mixture may also include water.
  • the substantially hydrocarbonaceous material is believed to be particularly effective in removing organic debris from the aluminum-containing article.
  • a specific example of such particularly useful component is Wax Emulsion M from Northwest Chemical Co.
  • the surfactant or combination of surfactants can be employed in the present compositions in concentrations which are effective to provide enhanced cleaning, i.e, relative to cleaning with a composition having no such surfactant or surfactants.
  • the surfactant or combination of surfactants are employed at concentrations in the range of about 0.01% to about 2%, more preferably about 0.05% to about 1%, by weight of the composition.
  • One or more coupling agents may be included in the present compositions to provide increased homogeneity to the present composition (or to the concentrate from which the present composition is derived).
  • conventional coupling agents such as butyl cellosolve, isopropyl alcohol and the like.
  • the present composition is applied to the debris-laden aluminum-containing article at comparatively low to moderate temperatures.
  • Preferred composition/aluminum-containing article contacting temperatures are in the range of about 60° F. to about 150° F. with lower temperatures, e.g., about 60° F. to about 110° F. being particularly useful to provide effective cleaning while having no substantial adverse impact on, e.g., etching of, the aluminum-containing article.
  • the contacting of the aluminum-containing articles to be cleaned can be effected by flooding, immersing, dipping, spraying and the like.
  • the aluminum-containing article may be subjected to a rinse step, e.g., with liquid water, to obtain removal, or more complete removal, of the debris.
  • This rinse can be effected by flooding, immersing, dipping, spraying and the like of the article with or in the rinse material, e.g., at the temperatures noted above.
  • the aluminum-containing article is recovered and has a reduced amount, i.e., relative to the original debris-laden article, of debris on its surface.
  • composition has prepared by blending together the various components with stirring:
  • This composition was tested as an aluminum cleaner by immersing a formed aluminum beverage can in the composition for about 15 minutes, at ambient temperature, i.e., about 70° F. to about 75° F., unless otherwise noted.
  • This formed aluminum beverage can was contaminated by smut, a mixture including aluminum and alumina fines and fatty acid residues from the lubricant used in forming the can.
  • This immersion or washing step was followed by a rinsing step in which the can was removed from the composition and placed in a bath of water, for about 15 minutes at ambient temperatures and then removed. Visual observation was used to determine the effectiveness of the composition as an aluminum cleaner.
  • composition provided some smut removal during the washing step. Substantially all of the remaining smut was removed during the rinsing step so that a clean aluminum beverage can resulted. Moreover, except for smut removal, the can was substantially unaffected by the treatment. For example, no evidence of aluminum etching was observed. Such etching is undesirable and has often occurred in the past with cleaning compositions including relatively large concentrations of strong acids, such as sulfuric acid, hydrofluoric acid and the like.
  • Example 1 was repeated except that the final composition included an additional 4.4% by weight of the levo form of tartaric acid.
  • the cleaning results obtained with this composition were similar to the results obtained in Example 1. For example, substantially no additional smut removal was obtained during the washing step.
  • the racemic form of tartaric acid is more effective that the levo form in the present invention.
  • compositions were prepared by blending together various components. Each of these compositions included the following:
  • compositions were used as an aluminum beverage can cleaner as outlined in Example 1.
  • Example 15 The following composition, Example 15, was prepared by blending together the following components:
  • Example 16 a composition as set forth above was similarly prepared except that the Surfactant IV was replaced by a commercially available blend of anionic surfactants (Surfactant VI) which included ammonium laurel sulfate; lauramide diethanol amine; sodium lauroyl sarcosinate; and isostearamide propyl ethyl diammonium ethosulfate.
  • Surfactant VI anionic surfactants
  • Example 17 a composition as set forth in Example was similarly prepared except that 4 gms. of a commercially available mixture of water, dodecyl benzene sulfonic acid (anionic) and paraffinic mineral oil (Surfactant VII) was included.
  • Example 18 a composition as set forth in Example was similarly prepared except that 4 gms. of a commercially available anionic material including sodium linear alkyl sulfonate (Surfactant VIII) was included.
  • a commercially available anionic material including sodium linear alkyl sulfonate Surfactant VIII
  • Example 19 a commercially available material including sodium n-hexadecyl diphenyloxide disulfonate (Surfactant IX) was used.
  • Example 20 a commercially available material including octyl phenoxy polyethoxy ethanol (Surfactant X) was used.
  • Example 21 a commercially available material including nonyl phenoxy poly (ethyleneoxy) ethanol (Surfactant XI) was used.
  • Example 22 a commercially available material including aliphatic polyalkoxylates (Surfactant XII) was used.
  • a cleaning composition was prepared by combining Concentrate A, at a rate of 9 fluid oz. per gallon, and Concentrate B, at a rate of 1.2 fluid oz. per gallon, with water.
  • the resulting clear composition was tested as an aluminum beverage can cleaner as set forth in Example 1. All of the smut was removed from the can, and no foaming problems were encountered.
  • the cleaner can be manufactured as two, or more, substantially clear (homogeneous) concentrates, which are then shipped to the cleaning site, combined with water and made ready for use as an aluminum cleaner.
  • the following acid composition was prepared by blending together the following components:
  • a series of six (6) enzymes were selected for testing to determine the effect of the enzyme in aluminum cleaning. Each enzyme was included in a composition which had the following make-up:
  • compositions were prepared by blending the following components together:
  • Example 1 Each composition was tested as an aluminum cleaner in accordance with the procedure outlined in Example 1. In addition, the foaming characteristics of the composition were observed.
  • compositions were prepared and tested as aluminum cleaners in accordance with the procedure outlined in Example 1 to illustrate the beneficial effect on aluminum cleaning of certain silicon-based materials.
  • Each of these compositions was prepared by adding 0.5 gm. of the specific silicon-based material being tested to 23 ml of the acid composition described in Examples 24 to 29. At this point, the mixture was observed for compatibility. After this observation, the mixture was combined with 300 g of water and tested as an aluminum cleaner.
  • a concentrate was prepared by blending together the following components:
  • a composition was prepared by blending together 2 g of this concentrate, 23 g of the acid composition of Example 24 to 29 and 300 ml of water.
  • This composition is tested as an aluminum cleaner in accordance with the procedure outlined in Example 1, and is found to provide excellent aluminum cleaning.
  • Example 44 Two samples of the composition of Example 44 were prepared for testing. One of the samples included 100 ppm (by weight) of fluoride ion.
  • composition samples were tested as follows:
  • the other piece of aluminum was immersed in the composition sample with the added fluoride at 130° F. for 7 minutes. Not only was the black smut completely removed, but also the aluminum piece became bright and shiny.
  • compositions can be used to clean up aluminum that has been etched in a caustic solution.
  • fluoride ion preferably at low concentrations in the range of about 1 ppm to about 500 ppm by weight, enhances the aluminum cleaning action of the present corporation.

Abstract

A composition and process for cleaning an aluminum-containing article is disclosed. The process comprises contacting a debris-laden aluminum-containing article with a composition at conditions effective to do at least one of the following: (1) remove at least a portion of the debris from the aluminum-containing article and (2) condition at least a portion of the debris for removal from the aluminum-containing article. The composition comprises water; at least one polycarboxylic acid component selected from the group consisting of polycarboxylic acids, salts of polycarboxylic acids and mixtures thereof; at least one acidic component in an amount effective to increase the solubility of the polycarboxylic acid component in the composition; and at least one acid acting enzyme in an amount effective to at least facilitate the removal of debris from an aluminum-containing article contacted with the composition.

Description

RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 251,299 filed Sept. 30, 1988, now pending.
BACKGROUND OF THE INVENTION
This invention relates to a composition and process useful for cleaning aluminum-containing articles. More particularly, the invention relates to a composition and process for removing debris, e.g., smut, unwanted deposit material, soil and the like, from such articles, e.g., aluminum foodstuff or beverage containers or cans.
Aluminum-containing articles are often formed into shapes using lubricants to assist in the forming process. For example, one or more lubricants are often employed in the drawing and ironing of aluminum container bodies of the type used to package foodstuffs and beverages. The forming processing itself and/or the lubricant or lubricants employed produce debris, e.g., as noted above, on the article which interferes with the over-all appearance of the article. In certain instances, this debris is referred to as smut. In general, such smut or smut-like material includes aluminum and/or alumina fines and/or lubricant material and/or lubricant residue. Such debris should be removed to provide an aluminum-containing article which is visually pleasing and, more importantly, make the article suitable for use, e.g., as a foodstuff or beverage container.
Various compositions have been suggested for use in cleaning aluminum articles. For example, King, et al U.S. Pat. No. 4,599,116 discloses an aqueous alkaline (a pH of at least 10) cleaning composition containing an alkalinity agent present in an amount to achieve removal of aluminum fines, a complexing agent, and one or more surfactants. Preferred alkalinity agents include alkali metal hydroxides and alkali metal carbonates. Among the complexing agents are gluconic acid, citric acid, glucoheptonic acid, sodium triphosphate, EDTA, tartaric acid or the like, as well as the soluble and compatible salts thereof and mixtures thereof. The relatively strong alkalinity agents employed could harm, e.g., etch, the aluminum surface unless care was exercised to control the cleaning operation.
Dollman U.S. Pat. No. 4,370,173 discloses removing lubricating oils and aluminum fines from aluminum surfaces using an aqueous solution of sulfuric and hydrofluoric acids and an anionic surfactant. Michelson, et al U.S. Pat. No. 3,448,055 discloses removing smut from aluminum with an aqueous composition including nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid and a surfactant. Such solutions of strong acids are effective to clean the aluminum 15 surfaces, but also tend to etch the surface as well. Such etching is undesirable.
Earhart U.S. Pat. No. 4,713,119 discloses removing alkali metal aluminum silicate deposits from chemical processing equipment by alternating treatments with acidic and basic solutions. The acidic solution contains sulfuric acid, sodium bisulfate, tartaric acid or phosphoric acid. This patent does not disclose cleaning aluminum-containing surfaces nor that the acidic solution includes a surfactant.
Wood, et al U.S. Pat. No. 4,264,418 discloses removing oxide film from metals or alloys containing iron, nickel, copper, beryllium, chromium, gold, zinc, lead, or tin with a composition containing gluconic acid or its alkali metal salts, citric acid or its alkali metal salts, or tartaric acid or its alkali metal salts and, preferably, a non-ionic surfactant. Aluminum-containing articles are not disclosed. Further, no "strong" acid is included in the composition.
Laporte, et al U.S. Pat. No. 3,306,773 discloses treating sintered aluminum parts with an aqueous alkaline solution before putting such parts into heat transfer surface. Pikaar U.S. Pat. No. 3,211,659 discloses acids, such as acetic acid, EDTA, citric acid, tartaric acid, gluconic acid, glyceric acid, malic acid, glycolic acid, saccharic acid, phosphoric acid, and benzoic acid for cleaning egg shells. Vinso U.S. Pat. No. 3,527,609 discloses the use of tartaric acid salts among salts of many polycarboxylic acids for use in cleaning cooling water systems. Rubin U.S. Pat. Nos. 4,049,467 and 4,129,423 disclose removing manganese derived discolorations from hard surfaces by use of either dihydroxy maleic acid, dihydroxy tartaric acid, their alkali metal salts, or mixtures thereof. None of these references is concerned with relatively heavy duty cleaning of, e.g, smut removal from, aluminum surfaces.
Yamasoe et al U.S. Pat. No. 4,728,456 discloses an aluminum surface cleaner which is an aqueous highly acidic solution containing sulfuric acid and/or nitric acid, ferric ions, but no chromium or fluoride ions. Yamasoe et al discloses that the etching of the aluminum by the sulfuric acid or nitric acid is promoted by the ferric ions. Also, Yamasoe et al discloses that chelating agents, such as citric acid and tartaric acid, can be included to accelerate the aluminum etching rate.
SUMMARY OF THE INVENTION
A new composition and process for cleaning debris, in particular smut, from the surface of an aluminum-containing article had been discovered. This invention provides very effective and efficient cleaning, e.g., removal of debris, with little or no substantial adverse effect on, e.g., etching of, the surface being cleaned. Thus, although the present composition includes at least one relatively strong acid, e.g., sulfuric acid, such acid often acts as a solubilizing agent rather than as the primary cleaning agent in removing debris from the aluminum-containing surface. In short, the present composition is specifically designed to clean, and not to etch, aluminum-containing surfaces.
In one broad aspect, the present invention involves a process for cleaning debris from the surface of an aluminum-containing article. This process comprises contacting a debris-laden aluminum-containing article with a composition comprising water, at least one polycarboxylic acid and/or at least one salt thereof, at least one acidic component in an amount effective to increase the water solubility of the polycarboxylic acid and/or salt thereof, and at least one acid acting enzyme in an amount effective to at least facilitate the removal of debris from the surface of the aluminum-containing article; and recovering the aluminum-containing article having at least a portion of the debris removed therefrom The contacting occurs at conditions effective to do at least one of the following: remove at least a portion of the debris from the aluminum-containing article and condition at least a portion of the debris for removal from the aluminum-containing article. The composition may also include, or all or a portion of the enzyme may be replaced by, at least one acid compatible siloxane component in an amount effective to at least facilitate the removal of at least a portion of the debris from the aluminum-containing article. Further, the composition preferably includes at least one surface active component, i.e., surfactant.
The use of the present- enzymes and/or the siloxane components has been found to provide enhanced aluminum cleaning without substantial adverse effects on, e.g., etching of, the surface being cleaned The effective and beneficial use of enzymes in aluminum cleaning, especially in the relatively highly acidic present compositions, is unexpected. One particularly surprising feature of the present invention is the inclusion of acid-compatible siloxane components and the beneficial aluminum cleaning resulting therefrom. For example, other materials of the same general class, such as silanes, have not been found to provide such enhanced aluminum cleaning.
DETAILED DESCRIPTION OF THE INVENTION
The present compositions comprise water, at least polycarboxylic acid and/or salts thereof, at least one additional acidic component, and at least one acid acting enzyme and/or at least one acid compatible siloxane component. The water often, and preferably, acts as a carrier for the other components of the composition. Water preferably comprises a major amount, i.e., at least about 50%, by volume, and more preferably at least about 70% by volume, of the composition used to treat the aluminum-containing article. In certain instances, it is desirable to prepare the present compositions in the form of one or more concentrates, with reduced amounts of water. The use of such concentrate or concentrates reduces the cost of transporting the present composition to the cleaning site. Thus, the present compositions can be formulated at the cleaning site simply by combining the desired amounts of concentrate or concentrates and water.
In a particularly useful embodiment, two concentrates are prepared. One concentrate includes the polycarboxylic acid and/or salts thereof and the additional acidic component in water, while the other concentrate includes the enzymes and/or the siloxane component, preferably together with one or more surfactants. This is particularly useful in situations where it is difficult or impossible to include all the presently useful components in one concentrate which is substantially homogeneous, e.g., clear. For example, if the surfactant mixture includes a substantially hydrocarbonaceous component, e.g., a mineral oil component, such component has only limited water solubility and does not form a homogenous concentrate with the other components of the present composition. Also, the enzyme and/or siloxane component may not form a completely homogenous concentrate with the acid components. In this instance, the enzyme and/or siloxane component and/or surfactant are best employed as a separate concentrate which is combined with the other components at the cleaning site when the full amount of water is present.
The acid acting enzymes included in the present invention are present in an amount effective to at least facilitate the removal of debris from an aluminum-containing article contacted with the enzyme-containing composition. One enzyme or a combination of enzymes may be employed. Acid acting enzyme means an enzyme which is effective or active in an acidic environment, in particular in the present aluminum cleaning compositions. The exact nature of the enzymatic action is not fully understood, although aluminum cleaning benefits are obtained provided that the enzyme or enzymes are effective in the relatively highly acidic compositions of the present invention. Such compositions preferably have a pH in the range of about 0.5 to about 3, more preferably about 0.8 to about 2. Without wishing to limit the scope of the present invention to any particular theory of operation, it is believed that the present acid acting enzyme or enzymes act on at least a portion of the debris on the aluminum-containing article to change its character and thereby render it more easily removable from the surface of the aluminum-containing article.
Examples of suitable acid acting enzymes include: enzyme derived from the fermentation of B. licheniformis, such as that sold by Genecor under the trademark Rhozyme P-64; enzyme extracted from pineapple stems, such as that sold by Miles under the tradename Bromelain 1:10; and enzyme derived from the fermentation of Aspergillus niger, such as that sold by Miles under the trademark Milezyme APF-2000. The amount of enzyme in the present compositions is relatively minor. The enzyme is preferably present, if at all, in an amount in the range of about 0.0001% to about 0.5% by weight of the total composition. Excessive amounts of enzyme are to be avoided in view of the relatively high cost of such materials. Enzyme preparations which are commercially sold often include materials other than the active enzyme, and may include as little as about 10% by weight, or even less, of the active enzyme. The amounts of enzyme noted in this paragraph refer to the active enzyme.
The siloxane components included in the present invention are present in an amount effective to at least facilitate the removal of debris from an aluminum-containing article contacted with the siloxane component-containing composition. Acid compatible siloxane component means a siloxane component which is dispersible, preferably soluble, in the present composition. The present siloxane components are polymeric materials having the characteristic siloxane structure included in the polymer, e.g., the backbone of the polymer. Such polymeric materials may, and preferably do, include one or more substituents, e.g., on the siloxane repeating unit of the polymer. Such substituents may include, for example, carbon, hydrogen, oxygen and nitrogen atoms. The siloxane component is preferably selected to minimize, and more preferably to substantially avoid, chemical reaction, e.g., acid/base reaction, between the siloxane component and the acid or acids of the present composition. Thus, it is preferred that the siloxane component preferably be substantially free of reactive amino groups. Also, it is preferred that the siloxane component be substantially free of sulfur, in particular mercapto groups. Such mercapto-containing siloxane components have been found to not provide aluminum cleaning benefits to the extent exhibited by other siloxane components.
It is particularly surprising that the present siloxane components provide beneficial aluminum cleaning since other silicone polymers, such as the silanes, are much less effective, and even substantially ineffective, in providing enhanced aluminum cleaning. Both the siloxane components and the silane components are effective defoamers in the present compositions. This fact makes the aluminum cleaning benefits achieved with the siloxane components all the more unexpected.
Examples of suitable siloxane components include: gamma-amino propyl trimethyl siloxane, such as that sold by PCR, Incorporated under the trademark Prosil 220; and gamma-methoxy-acryloxy propyl trimethyl siloxane, such as that sold by PCR, Incorporated under the trademark Prosil 248 and that sold by Dow Corning under the trademark Z-6030. The amount of siloxane component in the present compositions is preferably relatively minor. The siloxane component is relatively present in an amount in the range of about 0.0001% to about 0.5%, more preferably about 0.0005% to about 0.2%, by weight of the total composition. Excessive amounts of the siloxane component are to be avoided in view of the relatively high cost of such materials.
The polycarboxylic acid component, i.e., one or more polycarboxylic acid and/or salts thereof, useful in the present invention provide substantial advantages. The polycarboxylic acid component is preferably present in an amount effective to at least facilitate at least one of the following: (1) remove at least a portion of the debris from the aluminum-containing article; and (2) condition at least a portion of the debris for removal from the aluminum-containing article. Polycarboxylic acid refers to a carboxylic acid having more than one functional hydroxyl group, preferably two or three functional hydroxyl groups. The polycarboxylic acid component preferably includes 2 to about 10 carbon atoms per molecule. Without wishing to limit the scope of the invention to any particular theory of operation, it is believed that this polycarboxylic acid component plays a substantial role or roles in removing debris from the aluminum-containing article. For example, in many instances the debris to be removed includes organic material, such as residues from lubricants, e.g., containing fatty acids, used in forming or shaping the aluminum-containing article. It is believed that the polycarboxylic acids and/or salts thereof are particularly effective in attacking this organic material, especially to reduce the ability of such organic material to adhere or cling to the aluminum-containing surface. By compromising this organic material, this polycarboxylic acids component is also believed to act to facilitate removing aluminum particles (which are often a part of the debris) from the surface. While the polycarboxylic acid component provides effective debris cleaning/conditioning action, this component is insufficiently strong or aggressive to attack the aluminum-containing surface itself. Thus, the debris is removed and the aluminum-containing surface remains substantially unaffected, e.g., unetched.
Among the suitable polycarboxylic acids are: citric acid, tartaric acid, saccharic acid, maleic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, diglycolic acid, phthalic acid and the like. The preferred polycarboxylic acid is tartaric acid, in particular the racemic form of tartaric acid.
Any suitable source of polycarboxylic acid and/or salts thereof may be employed. If a salt is used, it is preferred that the salt be an ammonium salt, an alkali metal salt, an alkaline earth metal salt or mixtures thereof, more preferably an alkali metal salt. A particularly useful source of tartaric acid component is cream of tartar or potassium hydrogen tartrate. The polycarboxylic acid component is present in an amount effective to function as described herein. Preferably, the polycarboxylic acid component is present in the composition in an amount in the range of about 0.1% to about 20%, more preferably about 2% to about 15%, by weight, calculated as the polycarboxylic acid.
Polycarboxylic acids and/or salts thereof often have relatively limited water solubility. Thus, the presently useful additional acidic component is present in an amount effective to increase the water solubility of such polycarboxylic acid component. Such additional acidic component preferably is stronger, i.e., has a larger disassociation constant, than the polycarboxylic acid being employed. Examples of suitable acidic components include sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, nitric acid, mixtures thereof and the like, with sulfuric acid, phosphoric acid and mixtures thereof being preferred.
Care should be exercised to avoid having excessive amounts of such additional acidic components present. Such excessive amounts of acidic components may interact with the aluminum-containing article and cause damage, e.g., etching, of the surface being cleaned. However, it should be noted that in a particularly useful embodiment of the present invention, the acidic component is present in an amount effective to solubilize aluminum fines which may be part of the debris to be removed from the aluminum-containing article. The amount of acidic component included in the present composition may vary over a wide range and depend on many factors, for example, on the particular acid or acids being employed, on the particular debris to be removed, on the chemical make-up of the present composition and on the particular cleaning application involved. In certain embodiments it is preferred to include sufficient acidic component to maintain a pH in the range of about 0.5 to about 3, more preferably about 0.8 to about 2, during the contacting step.
The present compositions preferably include at least one surface active component or surfactant. In general, such surface active component or components act to increase or enhance the effectiveness of the composition, e.g., as an aluminum cleaner. However, it is not all together clear how such component or components function in the present invention. Without wishing to limit the invention to any particular theory of operation, it is believed that the surface active component or components act to do at least one of the following: (1) assist in removing the organic portion of the debris from the surface of the aluminum-containing article; (2) aid in maintaining the homogeneity of the composition during use; and (3) aid in preventing or inhibiting redeposition of the removed debris onto the surface of the aluminum-containing article.
Any suitable surface active component or combination of such components may be employed in the present compositions. Such component is preferably nonionic or anionic, with anionic surfactants being particularly preferred. The surface active component preferably has a Hydrophile-Lipophile Balance (HLB ratio), i.e., the balance of the size and strength of the hydrophilic (water-loving or polar) and lipophilic (oil-loving or non-polar) groups of the molecules, of at least about 12, more preferably in the range of about 12 to about 15. For further information regarding the determination of the HLB number of surfactants and emulsifying agents, reference is made to a publication entitled "The Atlas HLB System", Third Edition, 1963, by Atlas Chemical Industries, Inc.
Surfactants suitable for use in the practice of the present invention include, for example, those having hydrophobic groups comprising alkyl phenols, linear alcohols, branched-chain alcohols, secondary alcohols, propylene oxide/propylene glycol condensates and the like; hydrophilic groups such as ethylene oxide, ethylene oxide/ethylene glycol condensates and the like, and may further contain capping groups such as propylene oxide, chloride, benzyl chloride, amines and the like.
Specific examples of useful surfactants include free acids of complex organic phosphate esters (e.g., Gafac RP 170 from GAF Corporation); block polymers of propylene oxide and ethylene oxide (e.g., Pluonic L-61 from BASF Wyandotte, Inc.); ethoxylates of secondary alcohols containing about 11 to about 15 carbon atoms per molecule (e.g., Tergital 15-S-3 from Union Carbide Corporation); blends of linear alkyl sulfates and ethoxylates of secondary alcohols (as noted above); blends of anionic surfactants including ammonium laurel sulfate, lauramide diethanol amine, sodium laurel sarcosinate, and propyl ethyl diammonium ethosulfate; sodium linear alkyl sulfonate (e.g., Darvan No.1 from R. T. Vanderbilt Company, Inc.); and the like. A particularly useful component, especially in combination with one or more other surface active components, comprises a mixture of one or more surfactants, especially anionic surfactants, such as dodecyl benzene sulfonic acid, together with at least one substantially hydrocarbonaceous material, such as paraffinic mineral oil. This mixture may also include water. The substantially hydrocarbonaceous material is believed to be particularly effective in removing organic debris from the aluminum-containing article. A specific example of such particularly useful component is Wax Emulsion M from Northwest Chemical Co. An aqueous material including dodecyl benzene sulfonic acid without paraffinic mineral oil, such as that sold by Northwest Chemical Co. under the trademark Northwest 3867, is also particularly useful.
The surfactant or combination of surfactants can be employed in the present compositions in concentrations which are effective to provide enhanced cleaning, i.e, relative to cleaning with a composition having no such surfactant or surfactants. Preferably, the surfactant or combination of surfactants are employed at concentrations in the range of about 0.01% to about 2%, more preferably about 0.05% to about 1%, by weight of the composition.
One or more coupling agents, e.g., conventional coupling agents such as butyl cellosolve, isopropyl alcohol and the like, may be included in the present compositions to provide increased homogeneity to the present composition (or to the concentrate from which the present composition is derived).
In accordance with the present invention, the present composition is applied to the debris-laden aluminum-containing article at comparatively low to moderate temperatures. Preferred composition/aluminum-containing article contacting temperatures are in the range of about 60° F. to about 150° F. with lower temperatures, e.g., about 60° F. to about 110° F. being particularly useful to provide effective cleaning while having no substantial adverse impact on, e.g., etching of, the aluminum-containing article. The contacting of the aluminum-containing articles to be cleaned can be effected by flooding, immersing, dipping, spraying and the like.
The aluminum-containing article may be subjected to a rinse step, e.g., with liquid water, to obtain removal, or more complete removal, of the debris. This rinse can be effected by flooding, immersing, dipping, spraying and the like of the article with or in the rinse material, e.g., at the temperatures noted above. In any event, after contact with the present composition, and the rinse step if desired or necessary, the aluminum-containing article is recovered and has a reduced amount, i.e., relative to the original debris-laden article, of debris on its surface.
The following non-limiting examples illustrate certain aspects of the present invention.
EXAMPLE 1
The following composition has prepared by blending together the various components with stirring:
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                   Wt %                                                   
______________________________________                                    
Water                92.5                                                 
Sulfuric Acid (25% by weight                                              
                     0.7                                                  
in water)                                                                 
Cream of Tartar (potassium                                                
                     6.5                                                  
bitartrate).sup.(1)                                                       
Surfactant I.sup.(2) 0.07                                                 
Surfactant II.sup.(3)                                                     
                     0.07                                                 
Surfactant III.sup.(4)                                                    
                     0.03                                                 
Surfactant IV.sup.(5)                                                     
                     0.13                                                 
                     100.00                                               
______________________________________                                    
 .sup.(1) This material includes tartaric acid functionality in the racemi
 form.                                                                    
 .sup.(2) A commercially available anionic material including a free acid 
 of a complex organic phosphate ester.                                    
 .sup.(3) A commercially available nonionic material including block      
 copolymers of propylene oxide and ethylene oxide.                        
 .sup.(4) A commercially available nonionic material including ethoxylates
 of secondary alcohols containing about 11 to about 15 carbon atoms per   
 molecule.                                                                
 .sup.(5) A commercially available blend of anionic and nonionic          
 surfactants, believed to be linear alkyl sulfates together with          
 ethoxylates of secondary alcohols as noted in (4) above.
This composition was tested as an aluminum cleaner by immersing a formed aluminum beverage can in the composition for about 15 minutes, at ambient temperature, i.e., about 70° F. to about 75° F., unless otherwise noted. This formed aluminum beverage can was contaminated by smut, a mixture including aluminum and alumina fines and fatty acid residues from the lubricant used in forming the can. This immersion or washing step was followed by a rinsing step in which the can was removed from the composition and placed in a bath of water, for about 15 minutes at ambient temperatures and then removed. Visual observation was used to determine the effectiveness of the composition as an aluminum cleaner.
The above-noted composition provided some smut removal during the washing step. Substantially all of the remaining smut was removed during the rinsing step so that a clean aluminum beverage can resulted. Moreover, except for smut removal, the can was substantially unaffected by the treatment. For example, no evidence of aluminum etching was observed. Such etching is undesirable and has often occurred in the past with cleaning compositions including relatively large concentrations of strong acids, such as sulfuric acid, hydrofluoric acid and the like.
EXAMPLE 2
Example 1 was repeated except that the final composition included an additional 4.4% by weight of the levo form of tartaric acid. The cleaning results obtained with this composition were similar to the results obtained in Example 1. For example, substantially no additional smut removal was obtained during the washing step. Thus, it surprisingly appears that the racemic form of tartaric acid is more effective that the levo form in the present invention.
In both Example 1 and 2, heating the compositions had substantially no effect on the aluminum cleaning results.
EXAMPLE 3 TO 14
A series of compositions were prepared by blending together various components. Each of these compositions included the following:
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                 Wt. gms.                                                 
______________________________________                                    
Water              300                                                    
Sulfuric Acid (25% by                                                     
                   1.5                                                    
weight in water)                                                          
Surfactant V.sup.(6)                                                      
                   0.8                                                    
Surfactant I       0.3                                                    
Surfactant III     0.1                                                    
Butyl carbitol     0.3                                                    
(coupling agent)                                                          
______________________________________                                    
 .sup.(6) Similar to Surfactant II.
Additional components were included in the various compositions, as indicated below. Each of these compositions was used as an aluminum beverage can cleaner as outlined in Example 1.
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        Additional Component,                                             
                          Comments on                                     
Example.sup.(7)                                                           
        gms., (Wt %)      Cleaning                                        
______________________________________                                    
Test                                                                      
3       Formic acid 1.2 gms.(0.4%)                                        
                          No effective cleaning                           
4       Acetic acid 1.7 gms.(0.6%)                                        
                          No effective cleaning.                          
5       Sulfuric acid (25% by                                             
                          Cleaning did not work                           
        weight in water) 25 gms.                                          
                          well.                                           
        (7.6%)                                                            
6       Surfactant IV 3 gms.(1.0%)                                        
                          Cleaning did not work                           
                          well.                                           
7       Sulfuric acid (25% by                                             
                          Cleaning worked well.                           
        weight in water) 25 gms.                                          
                          Potential for harmful                           
        (7.6%) plus Surfactant IV                                         
                          aluminum etching was                            
        3 gms (0.9%)      present because of                              
                          relatively high                                 
                          concentration of H.sub.2 SO.sub.4.              
8       Propionic acid 10 gms.                                            
                          No effective cleaning                           
        (3.2%)                                                            
9       Butyric acid 10 gms.(3.2%)                                        
                          Not all butyric acid                            
                          soluble, substantial                            
                          cleaning observed.                              
10      Crotonic acid 10 gms.(3.2)                                        
                          Only 3 gms. of crotonic                         
                          acid soluble, no                                
                          effective cleaning                              
11      Hydroxy acetic acid 10 gms.                                       
                          Does not form clear                             
        (3.2%)            solution, no effective                          
                          cleaning.                                       
12      Sodium ethylene diamine                                           
                          Not soluble in                                  
        tetra acetate 10 gms.(3.2%)                                       
                          composition, did attack                         
                          smut when crystals                              
                          dissolved during                                
                          rinsing.                                        
13      Ascorbic acid 10 gms.(3.2%)                                       
                          Substantial cleaning                            
                          observed, not as                                
                          effective as with                               
                          cream of tartar                                 
                          composition.                                    
14      Citric acid 10 gms.(3.2%)                                         
                          No effective cleaning                           
______________________________________                                    
 .sup.(7) As a base line, the composition described above, with no        
 additional components, was tested as an aluminum beverage can cleaner. No
 effective cleaning was observed. These results indicate that various othe
 additive materials do not provide the combination of benefits, e.g.,     
 effective aluminum cleaning with little or no risk of aluminum damage,   
 achieved by the present composition and method. Further, it should be    
 noted that a cleaning composition which precipitates one of its component
 can be detrimental to the high speed cleaning operations often used in   
 producing aluminum articles, e.g., beverage cans.
As a base line, the composition described above, with no additional components, was tested as an aluminum beverage can cleaner. No effective cleaning was observed. These results indicate that various other additive materials do not provide the combination of benefits, e.g., effective aluminum cleaning with little or no risk of aluminum damage, achieved by the present composition and method. Further, it should be noted that a cleaning composition which precipitates one of its components can be detrimental to the high speed cleaning operations often used in producing aluminum articles, e.g., beverage cans.
EXAMPLES 15 TO 18
The following composition, Example 15, was prepared by blending together the following components:
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                 Wt., gms.                                                
______________________________________                                    
Water              --                                                     
Sulfuric acid (25% by                                                     
                   37                                                     
weight in water)                                                          
Cream of Tartar    20                                                     
Surfactant V       1.1                                                    
Surfactant I       0.4                                                    
Surfactant III     0.1                                                    
Surfactant IV      2                                                      
Butyl cellosolve   5                                                      
Isopropyl alcohol  5                                                      
Commercially available                                                    
                   0.03                                                   
defoaming agent                                                           
______________________________________
In Example 16, a composition as set forth above was similarly prepared except that the Surfactant IV was replaced by a commercially available blend of anionic surfactants (Surfactant VI) which included ammonium laurel sulfate; lauramide diethanol amine; sodium lauroyl sarcosinate; and isostearamide propyl ethyl diammonium ethosulfate.
In Example 17, a composition as set forth in Example was similarly prepared except that 4 gms. of a commercially available mixture of water, dodecyl benzene sulfonic acid (anionic) and paraffinic mineral oil (Surfactant VII) was included.
In Example 18, a composition as set forth in Example was similarly prepared except that 4 gms. of a commercially available anionic material including sodium linear alkyl sulfonate (Surfactant VIII) was included.
Each of the above-noted compositions was tested as an aluminum beverage can cleaner as outlined in Example 1. Results of these tests are summarized as follows:
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Example       Comments on Cleaning Test                                   
______________________________________                                    
15            This composition provided                                   
              effective cleaning. Without                                 
              the water component, the                                    
              formula is an unstable                                      
              emulsion and therefore may                                  
              present handling problems.                                  
16            This composition provided                                   
              effective cleaning. The                                     
              dispersed smut in the                                       
              composition (after washing)                                 
              precipitated out of the                                     
              composition.                                                
17            This composition provided a                                 
              very clean can. Without the                                 
              water component, Surfactant                                 
              VII was not stable, i.e.,                                   
              did not from a homogenous                                   
              mixture with the other                                      
              components.                                                 
18            This composition did not clean                              
              as effectively as did the                                   
              composition of Example 17.                                  
              Thus, the paraffinic mineral                                
              oil may play a role in smut                                 
              removal.                                                    
______________________________________
EXAMPLES 19 TO 22
A base composition as prepared by blending together the various components with stirring:
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                Wt., Gms.                                                 
______________________________________                                    
Sulfuric acid (25% by                                                     
                  91                                                      
weight in water)                                                          
Cream of Tartar   49                                                      
Surfactant VIII   4                                                       
Surfactant IV     3                                                       
Commercially available                                                    
                  0.3                                                     
defoaming agent                                                           
______________________________________
In addition, a series of four (4) other surfactants were included, one in each of four (4) samples of the above-noted composition. These other surfactants were included in an attempt to produce a stable or clear concentrate which provided effective aluminum cleaning.
In Example 19, a commercially available material including sodium n-hexadecyl diphenyloxide disulfonate (Surfactant IX) was used. In Example 20, a commercially available material including octyl phenoxy polyethoxy ethanol (Surfactant X) was used. In Example 21, a commercially available material including nonyl phenoxy poly (ethyleneoxy) ethanol (Surfactant XI) was used. In Example 22, a commercially available material including aliphatic polyalkoxylates (Surfactant XII) was used.
Each of these concentrates was allowed to stand quiet for a period of time and then observed. Results of these observations are summarized as follows:
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Example      Observations                                                 
______________________________________                                    
19           This concentrate was clear.                                  
             However, when it was combined with                           
             additional water and used to clean                           
             aluminum beverage cans, as set for                           
             in Example 1, its cleaning                                   
             performance was poor relative                                
             to other compositions derived from                           
             cream of tartar.                                             
20           Concentrate was cloudy and                                   
             separated.                                                   
21           Concentrate was very cloudy.                                 
22           Concentrate was cloudy and                                   
             separated.                                                   
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These results indicate that if all the components, other than a substantial portion of the water, are to be included in a single mixture it may be important to effectively stir the concentrate before combining it with water for aluminum cleaning. In addition, these results also indicate that if a clear composition is deemed necessary, e.g. for marketing purposes, it may be necessary to provide the concentrated form of the present composition as two or more concentrates.
EXAMPLE 23
Two separate concentrates were prepared blending together the following components:
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                 Wt %                                                     
______________________________________                                    
Concentrate A                                                             
Cream of tartar    35.3                                                   
Sulfuric acid (25% by                                                     
                   64.7                                                   
weight in water)                                                          
Density 1.39 gms/ml.                                                      
Concentrate B                                                             
Surfactant VII     72                                                     
Surfactant IV      20                                                     
Commercially available                                                    
                   1                                                      
defoaming agent                                                           
Density 0.93 gms/ml                                                       
______________________________________
Each of these concentrates was substantially clear. A cleaning composition was prepared by combining Concentrate A, at a rate of 9 fluid oz. per gallon, and Concentrate B, at a rate of 1.2 fluid oz. per gallon, with water. The resulting clear composition was tested as an aluminum beverage can cleaner as set forth in Example 1. All of the smut was removed from the can, and no foaming problems were encountered.
These results demonstrate one alternative to using a single non-homogeneous concentrate. Thus, the cleaner can be manufactured as two, or more, substantially clear (homogeneous) concentrates, which are then shipped to the cleaning site, combined with water and made ready for use as an aluminum cleaner.
While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.
EXAMPLES 24 TO 29
The following acid composition was prepared by blending together the following components:
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                Wt. %                                                     
______________________________________                                    
Sulfuric Acid (98%                                                        
                  10                                                      
by weight in water)                                                       
Sulfuric acid (25%                                                        
                  35                                                      
by weight in water)                                                       
Phosphoric acid (85%                                                      
                  45                                                      
by weight in water)                                                       
Creme of tartar   10                                                      
______________________________________
A series of six (6) enzymes were selected for testing to determine the effect of the enzyme in aluminum cleaning. Each enzyme was included in a composition which had the following make-up:
______________________________________                                    
Water                 300    g.                                           
Base Acid Composition 23     ml.                                          
Surfactant XIII.sup.(8)                                                   
                      0.5    g.                                           
Enzyme.sup.(9)        0.5    g.                                           
______________________________________                                    
 .sup.(8) A commercially available amonic surfactant including a mixture o
 water and dodecyl benzene sulfonic acid.                                 
 .sup.(9) Each enzyme was included as, and the weight based on, the       
 commercially available enzymecontaining preparation.
Each composition was tested as an aluminum cleaner in accordance with the test procedure outlined in Example 1.
Results of these tests were as follows:
______________________________________                                    
                     Cleanliness                                          
                               Compatibility                              
Example  Enzyme      Rating.sup.(16)                                      
                               Rating.sup.(17)                            
______________________________________                                    
24       A.sup.(10)  Excellent Excellent                                  
25       B.sup.(11)  Good      Good                                       
26       C.sup.(12)  Good      Poor                                       
27       D.sup.(13)  Fair      Poor                                       
28       E.sup.(14)  Poor      Poor                                       
29       F.sup.(15)  Poor      Fair                                       
______________________________________                                    
 .sup.(10) Enzyme derived from the fermentation of B. licheniformis.      
 Claimed to be more than 40% active at pH 3.0. Sold by Genecor under the  
 trademark Rhozyme P64.                                                   
 .sup.(11) Enzyme extracted from pineapple stems. Claimed to be effective 
 at pH 3.0. Sold by Miles under the trademark Bromelain 1:10.             
 .sup.(12) Enzyme derived from fermentation of Aspergillus niger. 100%    
 active at pH 3.0. Sold by Miles under the trademark Milezyme APF2000.    
 .sup.(13) Enzyme derived from fermentation of B. substilis. Claimed to be
 inactive at pH 3.0. Sold by Genecor under the trademark Rhozyme P53.     
 .sup.(14) Enzyme extracted from Carica papaya fruit. Is ineffective below
 pH 3.0. Sold by Miles under the trademark Papain 16000.                  
 .sup.(15) Enzyme is an alkaline proteaseserine endopeptidase. Is effectiv
 above pH 7.0. Sold by GistBrocades under the trademark Maxatase.         
 LS400,000.                                                               
 .sup.(16) Cleanliness rating was based on degree of soil removal from the
 can into the composition as indicated by the darkening of the composition
 and by the lack of aluminum fines or smut left on the can. "Excellent" wa
 taken as complete removal of fines and smut from the can, while "poor" wa
 taken to be little or no darkening of the composition and little or no   
 removal of fines and smut from the can.                                  
 .sup.(17) Compatibility rating was based on the ability of the enzyme to 
 mix with the anionic surfactant and/or acid composition and form a clear 
 solution or a stable emulsion.
These results demonstrate that acid active enzymes are effective to enhance aluminum cleaning. Also, care is to be exercised in selecting the acid active enzyme for use in the present invention if the materials from which the final cleaning compositions are derived, e.g., by blending with water, are to be clear solutions and/or stable emulsions.
EXAMPLES 30 TO 34
A series of (5) compositions were prepared by blending the following components together:
                                  EXAMPLE E                               
__________________________________________________________________________
            30   31   32   33   34                                        
__________________________________________________________________________
Water       300                                                           
               g 300                                                      
                    g 300                                                 
                         g 300                                            
                              g 600                                       
                                   g                                      
Acid Composition                                                          
            23 ml                                                         
                 23 ml                                                    
                      23 ml                                               
                           23 ml                                          
                                23 ml                                     
(as in Examples 24-29)                                                    
Enzyme A    0.5                                                           
               g                                                          
Surfactant XIII  0.5                                                      
                    g                                                     
Lithium salt of       0.1                                                 
                         g                                                
Fluoroalkylthionyl acid                                                   
Commercially available     0.2                                            
                              g 0.2                                       
                                   g                                      
food grade silicon-based                                                  
defoamer                                                                  
__________________________________________________________________________
Each composition was tested as an aluminum cleaner in accordance with the procedure outlined in Example 1. In addition, the foaming characteristics of the composition were observed.
Results of these tests were as follows:
______________________________________                                    
             Cleanliness  Foaming                                         
Example      Rating       Characteristics                                 
______________________________________                                    
30           Fair         No foam                                         
31           Excellent    Very high foam                                  
32           Excellent    High foam                                       
33           Excellent    Low foam                                        
34           Good         Low foam                                        
______________________________________
These results indicate that a silicon-based defoamer is useful in the present compositions to reduce foam. In addition, such silicon-based material may have a beneficial effect on the aluminum-cleaning ability of the composition.
EXAMPLES 35 TO 43
A series of compositions was prepared and tested as aluminum cleaners in accordance with the procedure outlined in Example 1 to illustrate the beneficial effect on aluminum cleaning of certain silicon-based materials.
Each of these compositions was prepared by adding 0.5 gm. of the specific silicon-based material being tested to 23 ml of the acid composition described in Examples 24 to 29. At this point, the mixture was observed for compatibility. After this observation, the mixture was combined with 300 g of water and tested as an aluminum cleaner.
Results of these observations and tests were as follows:
__________________________________________________________________________
     Silicon-based                                                        
               Acid                                                       
Example                                                                   
     Material  Compatibility                                              
                         Cleanability                                     
__________________________________________________________________________
35   gamma-amino                                                          
               Dispersion                                                 
                         Composition turned                               
     Propyl trimethyl                                                     
               formed    black and can become                             
     siloxane            clean during rinse                               
36   gamma-methoxy-                                                       
               Same as   Same as                                          
     acryloxy Propyl                                                      
               Example 35                                                 
                         Example 35                                       
     trimethyl siloxane                                                   
37   gamma-methoxy-                                                       
               Same as   Same as                                          
     acryloxy Propyl                                                      
               Example 35                                                 
                         Example 35                                       
     trimethyl siloxane                                                   
     (different source)                                                   
38   organofunctional                                                     
               Clear solution                                             
                         Composition turned                               
     silane              very black and can                               
                         did not rinse clean                              
39   organofunctional                                                     
               Clear solution                                             
                         Composition turned                               
     silane              slightly black and                               
     (different source)  can did not rinse                                
                         clean                                            
40   gamma-mercapto                                                       
               Dispersion                                                 
                         Same as Example 39                               
     Propyl trimethyl                                                     
               formed                                                     
     siloxane                                                             
41   gamma-mercapto                                                       
               Clear     Very poor cleaning                               
     Propyl trimethyl                                                     
               solution                                                   
     siloxane                                                             
     (different source)                                                   
42   N-beta-aminoethyl                                                    
               Violent reaction-                                          
                         Not tried                                        
     gamma-amino                                                          
               neutralization of                                          
     Propyl trimethyl                                                     
               amine and                                                  
     siloxane  production of                                              
               gummy residue                                              
43   Acrylic   Material  Not tried                                        
     modified silane                                                      
               solidified                                                 
__________________________________________________________________________
The results indicate that acid compatible, sulfur-free siloxane materials provide beneficial aluminum cleaning. In contrast, the silanes and the mercapto siloxanes, although acid compatible and possibly effective defoamers, do not provide such beneficial aluminum cleaning effects. Care is to be exercised to avoid siloxane materials which react, e.g., in an acid/base neutralization reaction, with the acid or acids present in the composition.
EXAMPLE 44
A concentrate was prepared by blending together the following components:
______________________________________                                    
                 Wt. %                                                    
______________________________________                                    
Sulfactant XIII    34.4                                                   
Enzyme A           8.5                                                    
Lithium salt of                                                           
fluoroalkylthionyl acid                                                   
                   2.0                                                    
Sulfactant IV      6.1                                                    
gamma-amino Propyl                                                        
trimethyl siloxane 1.0                                                    
Water              48.0                                                   
______________________________________
A composition was prepared by blending together 2 g of this concentrate, 23 g of the acid composition of Example 24 to 29 and 300 ml of water.
This composition is tested as an aluminum cleaner in accordance with the procedure outlined in Example 1, and is found to provide excellent aluminum cleaning.
EXAMPLES 45 AND 46
Two samples of the composition of Example 44 were prepared for testing. One of the samples included 100 ppm (by weight) of fluoride ion.
The composition samples were tested as follows:
Two pieces of aluminum were dipped in concentrated chlorine-based bleach solution overnight. A black, smutty material became etched on these aluminum pieces as a result of this dipping.
One piece of aluminum was immersed in the composition sample without added fluoride ion at 130° F. for 10 minutes. The black smut was completely removed.
The other piece of aluminum was immersed in the composition sample with the added fluoride at 130° F. for 7 minutes. Not only was the black smut completely removed, but also the aluminum piece became bright and shiny.
These results indicate that the present compositions can be used to clean up aluminum that has been etched in a caustic solution. The addition of fluoride ion, preferably at low concentrations in the range of about 1 ppm to about 500 ppm by weight, enhances the aluminum cleaning action of the present corporation.
While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims.

Claims (22)

WHAT IS CLAIMED IS;
1. A composition useful for cleaning debris from an aluminum-containing article comprising: water; at least one polycarboxylic acid component selected from the group consisting of polycarboxylic acids, salts of polycarboxylic acids and mixtures thereof; at least one acidic component in an amount effective to increase the solubility of said polycarboxylic acid component in said composition; and at least one acid acting enzyme in an amount effective to at least facilitate the removal of debris from an aluminum-containing article contacted with said composition.
2. The composition of claim 1 wherein said polycarboxylic acid component is present in an amount effective to at least facilitate at least one of the following: (1) remove at least a portion of said debris from said aluminum-containing article; and (2) condition at least a portion of said debris for removal from said aluminum-containing article.
3. The composition of claim 1 wherein said polycarboxylic acid component is selected from the group consisting of racemic tartaric acid, salts of racemic tartaric acid and mixtures thereof.
4. The composition of claim 1 wherein said acidic component is selected from the group consisting of sulfuric acid, phosphoric acid and mixtures thereof.
5. The composition of claim 4 which further comprises about 1 ppm to about 500 ppm by weight of fluoride ion.
6. The composition of claim 1 which further comprises at least one surface active component selected from the group consisting of nonionic surfactants, anionic surfactants and mixtures thereof.
7. The composition of claim 1 which further comprises at least one acid compatible, siloxane component in an amount effective to at least facilitate the removal of at least a portion of said debris from said aluminum-containing article.
8. The composition of claim 7 wherein said acid compatible, siloxane component is substantially sulfur free.
9. A composition useful for cleaning debris from an aluminum-containing article comprising: water; at least one polycarboxylic acid component selected from the group consisting of polycarboxylic acids, salts of polycarboxylic acids and mixtures thereof; at least one acidic component in an amount effective to increase the solubility of said polycarboxylic acid component in said composition; and at least one acid compatible, siloxane component in an amount effective to at least facilitate the removal of at least a portion of said debris from said aluminum-containing article.
10. The composition of claim 9 wherein said acid compatible, siloxane component is substantially sulfur free.
11. The composition of claim 9 wherein said polycarboxylic acid component is present in an amount effective to at least facilitate at least one of the following: (1) remove at least a portion of said debris from said aluminum-containing article; and (2) condition at least a portion of said debris for removal from said aluminum-containing article.
12. The composition of claim 9 wherein said polycarboxylic acid component is selected from the group consisting of racemic tartaric acid, salts of racemic tartaric acid and mixtures thereof.
13. The composition of claim 9 wherein said acidic component is selected from the group consisting of sulfuric acid, phosphoric acid and mixtures thereof.
14. The composition of claim 13 which further comprises about 1 ppm to about 500 ppm by weight of fluoride ion.
15. The composition of claim 9 which further comprises at least one surface active component selected from the group consisting of nonionic surfactants, anionic surfactants and mixtures thereof.
16. A process for cleaning debris from the surface of an aluminum-containing article comprising:
contacting a debris-laden aluminum containing article with a composition at conditions effective to do at least one of the following: (1) remove at least a portion of said debris from said aluminum-containing article and (2) condition at least a portion of said debris for removal from said aluminum containing article, said composition comprising water; at least one polycarboxylic acid component selected from the group consisting of polycarboxylic acids, salts of polycarboxylic acids and mixtures thereof; at least one acidic component in an amount effective to increase the solubility of said polycarboxylic acid component in said composition; and at least one acid acting enzyme in an amount effective to at least facilitate the removal of debris from said aluminum-containing article; and
recovering said aluminum-containing article having at least a portion of said debris removed therefrom.
17. The process of claim 16 wherein said polycarboxylic acid component is present in an amount effective to at least facilitate at least one of the following: (1) remove at least a portion of said debris from said aluminum-containing article; and (2) condition at least a portion of said debris for removal from said aluminum-containing article.
18. The process of claim 16 wherein said polycarboxylic acid component is selected from the group consisting of racemic tartaric acid, salts of racemic tartaric acid and mixtures thereof.
19. The process of claim 16 wherein said composition further comprises at least one acid compatible, siloxane component in an amount effective to at least facilitate the removal of at least a portion of said debris from said aluminum-containing article.
20. A process for cleaning debris from the surface of an aluminum-containing article comprising:
contacting a debris-laden aluminum containing article with a composition at conditions effective to do at least one of the following: (1) remove at least a portion of said debris from said aluminum-containing article and (2) condition at least a portion of said debris for removal from said aluminum containing article, said composition comprising water; at least one polycarboxylic acid component selected from the group consisting of polycarboxylic acids, salts of polycarboxylic acids and mixtures thereof; at least one acidic component in an amount effective to increase the solubility of said polycarboxylic acid component in said composition; and at least one acid compatible, siloxane component in an amount effective to at least facilitate the removal of at least a portion of said debris from said aluminum-containing article.
21. The process of claim 20 wherein said acid compatible, siloxane component is substantially sulfur free.
22. The process of claim 20 wherein said polycarboxylic acid component is selected from the group consisting of racemic tartaric acid, salts of racemic tartaric acid and mixtures thereof.
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US5269957A (en) * 1991-02-18 1993-12-14 Taiho Industries Co., Ltd. Rust removing agent for stainless steel surface
WO1995021230A1 (en) * 1994-02-03 1995-08-10 The Procter & Gamble Company Maleic acid-based aqueous cleaning compositions and methods of using same
WO1996038238A1 (en) * 1995-05-30 1996-12-05 Henkel Corporation Acidic cleaning composition and process for aluminiferous metals
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US20040099285A1 (en) * 2002-11-25 2004-05-27 Applied Materials, Inc. Method of cleaning a coated process chamber component
US7964085B1 (en) 2002-11-25 2011-06-21 Applied Materials, Inc. Electrochemical removal of tantalum-containing materials
US6902628B2 (en) * 2002-11-25 2005-06-07 Applied Materials, Inc. Method of cleaning a coated process chamber component
US20040152614A1 (en) * 2003-01-23 2004-08-05 Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) Cleaner composition for formed metal articles
US9447507B2 (en) 2003-01-23 2016-09-20 Henkel Ag & Co. Kgaa Cleaner composition for formed metal articles
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US7348302B2 (en) 2004-11-08 2008-03-25 Ecolab Inc. Foam cleaning and brightening composition comprising a sulfate/bisulfate salt mixture
US20060100119A1 (en) * 2004-11-08 2006-05-11 Ecolab, Inc. Foam cleaning and brightening composition, and methods
US20060105182A1 (en) * 2004-11-16 2006-05-18 Applied Materials, Inc. Erosion resistant textured chamber surface
US8021743B2 (en) 2004-11-24 2011-09-20 Applied Materials, Inc. Process chamber component with layered coating and method
US20060110620A1 (en) * 2004-11-24 2006-05-25 Applied Materials, Inc. Process chamber component with layered coating and method
US20100086805A1 (en) * 2004-11-24 2010-04-08 Applied Materials, Inc. Process chamber component with layered coating and method
US7579067B2 (en) 2004-11-24 2009-08-25 Applied Materials, Inc. Process chamber component with layered coating and method
US8617672B2 (en) 2005-07-13 2013-12-31 Applied Materials, Inc. Localized surface annealing of components for substrate processing chambers
US9481608B2 (en) 2005-07-13 2016-11-01 Applied Materials, Inc. Surface annealing of components for substrate processing chambers
US7762114B2 (en) 2005-09-09 2010-07-27 Applied Materials, Inc. Flow-formed chamber component having a textured surface
US7981262B2 (en) 2007-01-29 2011-07-19 Applied Materials, Inc. Process kit for substrate processing chamber
US20080248213A1 (en) * 2007-03-30 2008-10-09 International Business Machines Corporation Release layer for imprinted photocationically cured films
US20080241418A1 (en) * 2007-03-30 2008-10-02 International Business Machines Corporation Release layer for imprinted photocationic curable resins
US7749422B2 (en) * 2007-03-30 2010-07-06 International Business Machines Corporation Release layer for imprinted photocationic curable resins
US8980045B2 (en) 2007-05-30 2015-03-17 Applied Materials, Inc. Substrate cleaning chamber and components
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